JPS59199863A - Production of surface modified substance - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized in that coarse-grained sand, lp
Concerning a method for modifying the surface of coarse sand, fiber hair, etc. by making a synthetic resin a nuclide without contacting the surface of fibers, fibers (, fn hair, etc.) with individual particles, single IP, etc. It is.

Conventionally, the material was synthetic %i such as polyester (KJi hair was less hydrophilic than animal hair, and the synthetic line ΔM hair was prototyped as a comb), which did not hold ink well and frequently broke ink while writing, making it unsuitable for practical use. (・However, polyester fiber wool has a stronger elasticity than animal hair, as is clear from Young's modulus.) It has the advantage of being a light that cannot be thrown away.

Therefore, in order to make polyester fibers hydrophilic, if a bath liquid or a self-curing resin solution containing a volatile solvent such as polyamide 4, cellulose, or protein is applied and dried and solidified, each single fiber will be the same. , d will form a clump of stuck fiber hairs.This means that no matter how dilute the resin solution concentration is, each monofaH'J It is possible to avoid adhesion of the comrades.Conversely, if you wash the fibers with color until the adhesion is completely dissolved, it will form on the surface of the fibers. It is a well-known basic principle that even the synthetic resin layer that has been washed away will be washed away.

The present invention takes the above points into consideration, and the polymerization catalyst, which is not a local molecule, is applied to the fibers whose surfaces are in free contact with each other at 41°C.
Each of the four fibers can be present on the surface of hair etc. without sticking to each other, and polymerization will proceed only where the catalyst is present, and the catalyst will not be leached into the monomer or single pile solution. Based on the premise that the transferred mating progresses in a non-uniform system, the X:i The present invention provides a method for modifying the surface of hair fibers.

Furthermore, the method according to the present invention is not only a method for imparting hydrophilicity to the surface of synthetic fiber bristles for the purpose of textiles, but also a method for imparting lipophilicity (hydrophobicity) to the surface of synthetic fibers. The method of forming a cable trunk and the object of forming a synthetic resin layer are not only fibers but also lenses, films, sheet foils, etc.
In traditional painting methods such as spheres and granular sand, the constituent units adhere to each other, resulting in K's 71. The present invention also suggests a method of modifying the surface of a material that would otherwise be damaged by forming a synthetic resin layer on the surface.

The technical content of the present invention will be explained based on experiments and examples below.The synthetic fiber hair material is polyester fiber hair with a tapered tip like animal hair and has a length of 50 mm. A fiber with a diameter of about 50 mm with a base thickness of 2.5 mil is used, and the synthetic resin layer added to the surface is made of polytetrahydrobilane-2,6, a newly developed hydrophilic polyamide. −
This polybicyclic oxalactam is a polybicyclic oxalactam, which has the following structure:
Polymerization method and resulting polybicyclic polymerization method in which bicyclic oxalactam having the chemical structure shown below, which is sahishikq [3,2,1,:)octan-7-one, is polymerized in a 7-ion manner as a monomer. For a detailed explanation of oxalactam, please refer to Hiroshi Sumitomo, “New Hydrophilic Nylon,” Engineering Research, Vol. 29, No. 8, 23.
Sada (1981), or Hiroshi Sumitomo, ``Hydrophilic Polyamide Model'', ``Hydrophilic Polyamide Model'', ``Hydrophilic Polyamide Preservation'' (193 pages of Itoka no Chemistry, Higashifugaku Publishing Co., Ltd. (1981), etc.) have been shown.

Polymerization catalysts include initiators and activators, and 1.Ii
The first initiator was the potassium salt of tetrahydrococctam under a stream of dry nitrogen, and the activator was the N-acetylated product of bicyclic oxalaccum, as shown in the following chemical structure. Synthesis and purification methods for certain O monomers, initiators, and activation materials are described by Hiroshi Sumitomo, Washin Hashimoto, Macromolecules, No. 10, 1327.
I basically used the method shown in Sada (1977).

Example Positive +1i3 synthesized under a stream of dry nitrogen and stored in a sealed tube
Weigh out 13.6 grams of monomer into an eggplant flask so that the initiator concentration is 2 mole percent based on the monomer, and degas at room temperature. O
・After repeating the dry nitrogen purge, bring it into the dry box.In addition to this, the dry box contains a sealed tube containing a catalyst, which is an initiator, and a screw stopper containing activated All. container, polyester fiber bundle, screw cap container containing solvent,
Bring in other equipment necessary for the operation, degas it to less than 2 mm of mercury for more than 1 hour, and then replace the drying with nitrogen.
The following operations are performed in the knee box.

Transfer the monopodal powder to a 100ml beaker and add 33
．． Dissolve the catalyst in 4 milliliters of tetrahydrofuran and add 165 microliters of activator using a microsyringe to make a single bath solution.
Initiator) Using a glass file, transfer the sealed tube to a 100 ml beaker, add 10 ml of tetrahydrofuran to the tip, dissolve and dry, and leave in a sagittarium mixture bath for 7 nights.

After immersing the polyester fiber bundle in the initiator solution, it was pulled up and brought into the dry box preparation room.

After drying by degassing under 2 mm of mercury or less, it is poured into a monomer solution and left for 1 hour. After removing the polyester fiber bundle from the monomer solution, it is stirred and washed with 100 ml of tetrahydrofuran in a 200 ml beaker, and then taken out from the dry box. 24 at 40 degrees Celsius and less than 3 mm of mercury after thorough washing.
Vacuum dry for more than an hour. In this case, the concentration of the initiator used in the T central vein is 2 mole percent based on the monomer, the concentration of the active emetic agent is also 1 mole percent based on the monomer, and the concentration of the solvent (tetrahydrofuran) is A'L]1 The mole fraction relative to -1 is 5.

Next, 3jly like the above? Using 10 polyester fiber bristles and untreated polyester fiber bristles, we made 10 prototypes of fine brushes with exactly the same specifications, and achieved a reading limit of 1.
u O, 1 mi! Using I-gram's direct chemical nature, we can calculate the weight of the car in a dry state, the additional weight when the tip is soaked with water, and the water contained in the tip (vl (on paper: lin).
<Weigh the weight of -i after absorbing it, calculate the weight of the water actually contained in i1, and the weight of the water that has migrated onto the filter paper, and calculate the amount of water absorbed and released, respectively. The arithmetic mean of the amount of water and the probability error were determined.
) (1) The water absorption amount was 8.91 ± 0.29 milligrams and the water separation amount was 3.41 ± 0.36 micrograms, whereas the polyester t'a fiber without any treatment The amount of water absorbed by the brush made of hair material was 7.41±0.25 milligrams, and the amount of water separation was 2.28±0.16 milliJ grams.

Therefore, if we consider the amount of water absorption to be the amount that can contain India ink and the amount of water repellency that can be expressed, the heavy chains made of polyester fibers treated as described above actually absorb ink This results in an improvement of about 20% in the amount of ink that can be contained, and an improvement of about 50% in the ability to type without cutting out the ink, and these values are close to or on the same level as brushes made of animal hair. It means that. Furthermore, the above-mentioned bicyclic oxalactam polymer obtained by separate polymerization was subjected to 2.
2.2-Polyester fiber bristles were dipped one by one in a solution dissolved in trifluoroethanol, dried one by one, and the obtained fiber bristles were bundled together to make a trial brush with the same specifications as above, and the same test as above was carried out. When I tried this, the water absorption jj, l was 8.8
9±0.21 milligrams and the amount of syneresis is 2.95+0.11
In milligrams, it showed the same value as the polyester fiber treated in the above example.

Here, it is unclear whether a layer of polybicyclic oxalactam is actually formed on the surface of the polyester filament bristles treated in the example, but from the appearance it appears that the polyester fiber inserts treated in the example are The polyester fibers treated with the above treatment are clearly more likely to get tangled in rainy weather than in sunny weather.
・It showed characteristics. Therefore, it is difficult to determine whether a polybicyclic oxalactam layer is formed on the surface simply from the appearance, but the monomer, initiator, and activator in the examples are easily soluble in tetrahydrofuran and water. However, since polybicyclic oxalactam does not dissolve in any of them, and the amount of water absorption and water separation was the same as that of the layer of polybicyclic oxalactam that was actually formed, it was found to be effective. It is interpreted that it actually forms a layer of polybicyclic oxalactam.

In addition, the amount of bound water and moisture absorption was measured using a differential scanning calorimeter (DSC) for the KIi polyester fiber treated in the example and the same polyester fiber before treatment. The results were as shown in the table below.

Before processing 0.6 section 1.5 section 6.8≠
0.7%fl): Measured after 12 hours f2):
71111 after 48:11 J1 From these results, it is clear that the treated polyester strain KB wool of the example has approximately 5 times the amount of bound water compared to the untreated one. It shows the southern inclusion rate of .

Next, assuming that polyamide exists on the surface of the polyester fiber
nd V, Rossbach), 7 Ngevantemakp Molecular Hemi (Angew, Makrom)
o ], chem, ), Vol. 86, pp. 203-213 (1
9'80) r = Determination of amine end groups in polyamide 6 and 6,6 by ninhydrin IRC, When tested using ninhydrin according to the method of J, the untreated product did not show any color development, but it was not carried out. The polyester fiber treated in the example was clearly colored, which indicates that the compound that is positive for the ninhydrin reaction, which is insensitive to water and tetrahydrofuran, and has an amine as a functional group, was treated in the example. Polynisdel irgA s+L
means that it exists.

Therefore, in this case, the reaction mechanism and other factors in the example are well known, and there is no room for uncertain factors to enter before and after the reaction. Therefore, the polyester fiber treated in the example is This means that polybicyclic oxalactam is formed in the coat of hair.

Furthermore, the method according to the present invention is effectively exhibited in so-called heterogeneous polymerization in which the polymer produced in the polymerization reaction is precipitated with R4 in the monomer solution. It is considered that the prerequisite is that the polymerization temperature is ℃・, which is not affected much by the magnitude of the polymerization reactivity. Therefore, in the case of the example, a bicyclic oxalactam with high polymerization reactivity was used and 1 ijl 0)'i! Although the opening time was longer during the polymerization, it is sufficient to make the 1jl longer during the polymerization even in the case of C. 2-pyrrolidone, ε-caprolactam, etc., which have lower polymerization reactivity.

In this case, bulk polymerization occurs, and in the case of 2-pyrrolidone, the polymerization temperature must be around 40 degrees Celsius, and in the case of ε-caprolactam, it must be at least 130 degrees Celsius.
Polymerization proceeds in a daze.

Next, the method according to the present invention can be applied not only to the anionic polymerization of lactams, but also to the radical polymerization of vinyl polymers such as acrylstyrene and butadiene, olefins, vinyl ethers, styrene derivatives, dienes, carbonyl compounds, cyclic nisfuls, etc. The furnace can be used for cationic polymerization, anionic polymerization, etc., and the synthetic Jl/d to be formed has not only hydrophobicity and hydrophobicity, but also adhesion, water repellency, (osseousness, etc.) depending on the purpose. It can be made to have a property.

Therefore, the method according to the present invention is different from the plasma polymerization method, which has recently begun to attract attention, which attempts to modify the surface of a material by causing a chemical reaction on the surface of the material using dry plasma or ultraviolet rays. First, a polymerization catalyst is present on the surface of the substance, and then a monomer is present, so that polymerization proceeds only on the surface of the substance where the catalyst is present, resulting in the production of a substance whose surface has the desired polymer properties. It is a method based on the conventional academic system of polymer synthesis that has already been established.

A method for producing a surface-modified material according to the present invention; c.
Therefore, there is a strong possibility that the plasma polymerization method and its purpose and effects may overlap in part, and I believe that this is the creation of an epoch-making technical idea that can be used in a wide range of applications.

Watch applicant: Shinwa Seisakusho Co., Ltd.

Claims (1)

[Claims] 1) In a polymerization system in which polymerization proceeds in a heterogeneous system, an object whose surface is to be modified is immersed in a solution of a polymerization catalyst, pulled out, and then dried. After making a thin solid polymerization catalyst exist on the surface of the object, it is immersed in a monomer solution to proceed with polymerization, and then immersed in a solution that decomposes and extracts substances other than the polymer. 41 A method for producing a surface-modified material that involves forming a synthetic resin film on the surface by stirring, washing, and drying. 2) The material whose surface is to be modified is tapered sharpened polyester fiber hair, and the single FTI solution is a solution consisting of a lactam and a catalytic amount of an activator called N-7 sillactam. 2. A method for producing a surface-modified material as claimed in claim 1, wherein the catalyst is an i3N initiator consisting of an alkali gold 17A salt of laczim, and the treatment is carried out under a stream of dry nitrogen.